Anchoring systems and methods utilizing acrylate compositions

ABSTRACT

This invention provides a composition for anchoring materials in or to masonry. The composition comprises a methacrylate ester monomer, a methacrylate ester polymer, a free-radical catalyst and a filler.

This is a continuation of application Ser. No. 08/310,709 filed on Sep. 21, 1994, now abandoned.

TECHNICAL FIELD

This invention relates to a composition for anchoring materials in or to concrete or masonry. More particularly, this invention relates to a methacrylate ester composition for anchoring materials in or to concrete or masonry.

BACKGROUND OF THE INVENTION

Many applications require that a material be anchored in or to concrete or masonry. For example, anchor bolts are employed in various fields of engineering as strengthening or reinforcing members in rock formations, or concrete or masonry structural bodies. The bolts, which are typically metallic, are inserted into holes in the rock formations, or concrete or masonry structural bodies, and are fixed or anchored therein by means of an anchor composition. Typically, the anchor composition cures or hardens (polymerizes) to form a strong bond between the rock formation, or the concrete or masonry structural body and the bolt. In concrete and masonry, anchor bolts are used for reinforcement. Anchor bolts are also used for attaching objects to concrete or masonry. Objects that have been attached to concrete or masonry using anchor bolts include, but are not limited to, electrical conduits, panels, piping and wall sections. Adhesive anchors are preferred over mechanical anchors for anchoring in soft concrete or masonry because adhesive anchors place less stress on the concrete or masonry. As used herein, the term "masonry" shall include, but is not limited to, stone, brick, ceramic tile, cement tile, hollow concrete block and solid concrete block.

A useful anchor composition should be inexpensive, provide for a strong bond between the concrete or masonry and the material to be anchored to the concrete or masonry, be easy to dispense at the location of use and have a long storage shelf life.

Some anchor compositions that have been used include compositions based on aromatic vinyl esters, aromatic polyesters and epoxies. These compositions can be expensive or may not provide the desired bond strength between the concrete or masonry and the material that is anchored in or to the concrete or masonry.

SUMMARY OF THE INVENTION

The present invention provides a composition for anchoring materials in or to concrete or masonry that comprises from about 20% to about 90% by weight of the entire composition of a methacrylate ester monomer/methacrylate ester polymer solution; a free-radical catalyst; and a filler.

In a preferred embodiment, the present invention provides a composition for anchoring materials in or to concrete or masonry that is made by mixing a first composition and a second composition. The first composition comprises from about 20% to about 90% by weight of the entire composition of a methacrylate ester monomer/methacrylate ester polymer solution; and a filler. The second composition comprises a free-radical catalyst.

DETAILED DESCRIPTION OF THE INVENTION

The present invention provides an anchor composition for anchoring materials in or to concrete or masonry. The materials to be anchored in or to concrete or masonry include, but are not limited to, metallic objects, such as steel bolts, ceramics, other concrete or masonry objects, plastics, glasses and woods.

The composition comprises methacrylate ester monomer, a methacrylate ester polymer, a free-radical catalyst and a filler. It may also be desirable to include in the composition a thixotropic agent, a chain transfer agent, a free-radical inhibitor, a fragrance, an activator, a promoter and/or a pigment. It is also recognized that other components known to those skilled in the art may be included in the composition. Such components may include, but are not limited to, surfactants, antifoaming agents, wetting agents, fungicides, impact modifiers, crosslinking agents and coupling agents.

The composition may be dispensed using various methods known to those skilled in the art. For example, the composition may be dispensed using a dual cartridge device similar to a caulk gun, or the composition may be dispensed using a glass capsule. The composition may also be dispensed in bulk from bulk containers using meter-mix equipment, which is known to those skilled in the art. U.S. Pat. Nos. 4,651,875, 4,706,806 and 4,729,696, the disclosures of which are hereby incorporated by reference, are directed to glass capsules. It is recognized that the amounts of the various components of the anchor composition may vary depending on the type of dispensing system used. In preferred dispensing methods, the anchor composition is formed by the mixing of a first composition and a second composition. Typically, the mixing occurs immediately before the anchor composition is to be used. For example, when the anchor composition is dispensed using a dispensing gun, the first composition and the second composition, which are contained in separate cartridges of the dispensing gun, may be mixed as they are ejected from the cartridges and applied to either the concrete or masonry, the material to be anchored to the concrete or masonry or both. Similarly, when the anchor composition is dispensed using a glass capsule, the capsule is typically comprised of two chambers that contain the first composition and the second composition respectively. When the glass capsule is crushed, the two chambers are crushed and the contents are allowed to mix, forming the anchor composition. Last, when the anchor composition is dispersed in bulk, a first composition and a second composition may be stored in separate bulk containers and combined through pumping with mixing in the appropriate ratio to make the anchor composition.

The anchor composition contains a methacrylate ester monomer and a methacrylate ester polymer. It is preferable if the methacrylate ester polymer has a weight-average molecular weight in the range of about 30,000 to about 120,000. More preferably, the polymer has weight-average molecular weight in the range of about 80,000 to about 120,000. In general, the methacrylate ester polymer is soluble in the methacrylate ester monomer to form a methacrylate ester monomer/methacrylate ester polymer solution, and the polymer is present in the range of about 10% to about 60% by weight of the methacrylate ester monomer/methacrylate ester polymer solution. Preferably, the polymer is present in the range of about 10% to about 40% of the methacrylate ester monomer/methacrylate ester polymer solution. Most preferably, the polymer is about 20% to about 30% by weight of the solution.

As used herein, the phrase "methacrylate ester monomer" shall mean esters of methacrylic acid, including, but not limited to, the methyl, ethyl, propyl, isopropyl, butyl, tert-butyl, cyclohexyl, 2-ethylhexyl and tetrahydrofurfuryl esters of methacrylic acid.

As used herein the phrase "methacrylate ester polymer" shall mean a polymer which can theoretically be made from methacrylate ester monomers. The polymer may be a homopolymer or a copolymer. If the polymer is a copolymer, the polymer may be, for example, a random, block, graft or alternating copolymer. The polymer also can be linear or branched and can be based on two or more methacrylate ester monomers.

It is also contemplated that the methacrylate ester monomer may be a mixture of different methacrylate monomers, and the methacrylate polymer may be a mixture of more than one polymer.

The monomer/polymer solution is present in the anchoring composition in the range of about 20% to about 90% by weight of the entire composition. Preferably, the monomer/polymer solution is present in the anchoring composition is an amount in the range of about 30% to about 60%. Most preferably, the polymer/monomer solution is about 40% by weight of the entire composition when the composition is dispensed using a dispensing gun and about 20% by weight of the entire composition when the composition is dispensed using a glass capsule.

The anchor composition also comprises a free-radical catalyst, which starts the free-radical polymerization of the methacrylate ester monomers in the composition, which results in a hardened or cured composition. Examples of free-radical catalysts include, but are not limited to, peroxides, such as the diacyl peroxides, hydroperoxides, peresters, peracids and radiant energy or thermal energy, i.e. ultraviolet light and heat. Examples of specific free-radical catalysts include, but are not limited to, dibenzoyl peroxide, cumene hydroperoxide, tertiary butyl peroxide, dicumyl peroxide, tertiary butyl peroxide acetate, tertiary butyl perbenzoate and ditertiary butyl azodiisobutyronitrile. Examples of the diacyl peroxides include, but are not limited to, dibenzoyl peroxide, succinic acid peroxide, dilauroyl peroxide, didecanoyl peroxide and diisononanoyl peroxide. The most preferred free-radical catalyst is dibenzoyl peroxide. It is also contemplated that more than one free-radical catalyst may be used in the composition. The free-radical catalyst is usually present in the composition in the range from about 0.5% to about 5% by weight of the entire composition. Preferably, the catalyst is found in the composition in the range of about 1% to about 3% by weight of the entire composition. Most preferably, the free-radical catalyst is about 2% by weight of the entire composition.

The composition can also include a catalyst activator (also called an initiator or a free radical accelerator). Throughout this application, the terms free radical accelerator, "activator" and "initiator" are used interchangeably. Representative activators include an aldehyde-amine condensation product, organic sulfonyl chlorides, tertiary amines or mixtures thereof. For example, such a condensation product can be made from butyraldehyde and a primary amine, such an amine being, for example, aniline or butylamine. Also suitable as activators are tertiary amines such as N,N-dimethyl aniline, N,N-dimethyl toluidine, N,N-diethylaniline, N,N-diethyl toluidine, N,N-bis(2-hydroxyethyl)-p-toluidine, N,N-bis(hydroxypropyl)-p-toluidine and the like. A preferred activator is N,N-bis(2-hydroxyethyl)-p-toluidine.

The composition can also include a promoter, which is an organic salt of a transition metal such as cobalt, nickel, manganese or iron naphthenate, copper octoate, copper acetylacetonate, iron hexoate or iron propionate.

In concrete anchoring, much of the heat of polymerization is lost to the mass of concrete. Therefore, activators such as N,N-bis(2-hydroxyethyl)-p-toluidine may be used to achieve the desired rapid cure times. However, when anchoring in hollow concrete blocks, portions of the anchor composition may not contact the concrete, and heat loss to the surroundings is minimized, which can result in incomplete curing of the bulk anchor composition. In such cases, it may be preferable to add a chain transfer agent to the composition. Chain transfer agents are discussed below. The amount of activator and chain transfer agent that gives acceptable cure speeds, shelf life and bulk cure properties for a particular application and composition can be determined by those skilled in the art by routine optimization.

The initiators and activators, if part of the composition can be added in an amount up to about 10% by weight of the entire composition. Preferred amounts are in the range of about 0.01 to about 1.5%. Promoters are typically used in amounts up to about 0.5% by weight of the composition, and preferably about 1 part per million to about 0.5% by weight of the entire composition.

The anchor composition may also comprise a thixotropic agent. A thixotropic agent that is added to a composition causes the composition to become more fluid, i.e. less viscous, when agitated, stirred or mixed or otherwise subjected to such shear forces. It is useful to include a thixotropic agent in the anchor composition to insure that the composition has the desired viscosity during application and after the composition is applied. In addition, a thixotropic agent may be added to an anchor composition to prevent the settling of other solid components of the composition and to increase the viscosity of the composition. The thixotropic agent also facilitates dispensing of the composition because when a shear force is applied, e.g. expulsion of the composition from a dispensing gun, the thixotropic agent makes the resulting composition less viscous, and therefore, more easy to expel from the cartridges of the dispensing gun. The thixotropic agent may be found in the anchor composition in an amount in the range of 0.5% to about 10% by weight of the entire composition. Preferably, the thixotropic agent is found in the composition in an amount in the range of about 2% to about 7% by weight of the entire composition. Most preferably, the thixotropic composition is about 5% when the composition is dispensed from a dispensing gun. Typically, no thixotropic agent is needed when the anchor composition is dispensed using a glass capsule. An example of a suitable preferred thixotropic agent is fumed silica. Also contemplated are the various silicas made by the various methods known in the art, including pyrolysis of silicon tetrachloride and precipitation. Other suitable thixotropic agents include the various organoclays and various fibers. In some anchor compositions, the thixotropic agent may also be considered a filler. A suitable silica thixotropic agent is Aerosil® R202, which may be obtained from the Degussa Corporation of Ridgefield Park, N.J. It is also contemplated that more than one thixotropic agent may be used in an anchor composition.

The anchor composition of the present invention also comprises one or more fillers. Fillers are typically added to compositions for various reasons, including to reduce shrinkage of the composition that may occur during polymerization and to reduce the cost of the composition, as fillers replace a portion of the more expensive components of an anchor composition. The filler may also provide for improved bond strength of the anchor composition when polymerized and help to prevent the settling out of other particulate materials in the composition. In generally, the filler is an inert, inorganic, solid, particulate compound. By inert it is meant that the filler does not detrimentally interact with any other component of the composition. Examples of suitable fillers include, but are not limited to, crushed glass, glass beads, quartz, silica, limestone, alumina, various clays, diatomaceous earth and other materials such as mica, flint powder, kryolite, alumina trihydrate, talc, sand, pyrophyllite, blanc fixe, granulated polymers such as polyethylene, hollow glass and polymer beads, zinc oxide, novaculite, calicum sulfate and mixtures thereof. Preferred fillers are quartz, glass and silica. Fillers may be treated with coupling agents to improve bonding to the polymer matrix. Examples of coupling agents which may be used to treat the fillers are silanes, titanates and zirconates. Fillers can be found in the composition in an amount in the range of 10% to about 75% by weight of the entire composition. Preferably, fillers are found in the range of about 30% to about 60% by weight of the entire composition. The exact particle size of the filler will depend on the desired consistency of the composition and the method for dispensing the anchor composition. For example, fillers having a large average particle size (300 microns and larger) may clog static mixers that are used in dispensing systems such as dispensing guns. On the other hand, fillers having a large particle size can be used in glass capsules. Preferred particle sizes are about 50 microns or larger. However, in cases where a filler is used to prevent the settling out of other particulate matter in a composition, a particle size smaller than 50 microns may be desked. It is also recognized that a filler having a particle size less than 50 microns may be used in combination with other fillers, some having particle sizes greater than 50 microns.

Preferred fillers for use in anchor compositions that are to be dispensed using a dispensing gun have average particle sizes in the range of about 50 to about 275 microns. Preferred fillers for use in anchor compositions that are to be dispensed using a glass capsule have average particles sizes in the range of about 100 to about 3,000 microns.

The anchor composition may also include a free-radical chain transfer agent. Free-radical chain transfer agents are included in anchor compositions to facilitate polymerization. Chain transfer agents also have the effect of limiting the molecular weight of the polymers that are formed by the polymerization. The use of a free-radical chain transfer agent provides for an acceptable polymerization speed and for more complete polymerization of the anchor composition, particularly when a large mass of the composition is to be polymerized. Preferred free-radical chain transfer agents include mercaptans such as dodecyl mercaptan. In addition, other chain transfer agents are known to those skilled in the art, and a suitable free-radical chain transfer agent may be readily selected by those skilled in the art. The free-radical chain transfer agent may be found in the composition in the range of about 0.1% to about 2% by weight of the entire composition. Preferably, the free-radical chain transfer agents is present in the composition in the range of about 0.25% to about 1%.

The anchor composition may also include a free-radical inhibitor. A free-radical inhibitor is added to a composition to inhibit the polymerization of monomers in the composition until such polymerization is desired. The addition of a free-radical inhibitor also increases the storage shelf life of the anchor composition.

In one embodiment of the present invention, the anchor composition is formed by mixing a first composition and a second composition. The first composition contains the polymerizable monomer and may contain an inhibitor to prevent polymerization of the monomer until desired, and the second composition contains a free-radical catalyst. When the first composition and the second composition are combined, polymerization occurs. Free-radical inhibitors are known to those skilled in the art. A preferred free-radical inhibitor is trimethyl hydroquinone. Other suitable free-radical inhibitors include, but are not limited to, hydroquinone, hydroquinone monomethyl ether, t-butyl catechol and naphthaquinone. It is also contemplated that more than one free radical inhibitor may be employed in the anchor composition. Typically, the free-radical inhibitor may be found in the composition in an amount in the range of about 0.001% to about 0.1% by weight of the entire composition.

The anchor composition may also contain a fragrance. A fragrance is used in an anchoring composition to mask any odor of the composition that is thought undesirable or unpleasant. A preferred fragrance is Atlanta Fragrance 16332. Similarly, a pigment may be employed to color the anchoring composition. Suitable pigments are known to those skilled in the art.

In a preferred embodiment the anchor adhesive is made by mixing a first composition and a second composition. The first composition comprises a methacrylate ester monomer, a methacrylate ester polymer and a filler. The first composition may also comprise a thixotropic agent, a chain transfer agent, a free-radical inhibitor, a fragrance, an activator, a promoter and/or a pigment. The second composition contains a free radical catalyst. The second composition may also include a filler, a thixotropic agent, a fragrance, a plasticizer, and/or a pigment. It is also contemplated that both the first composition and the second composition may contain some of the same components.

The ratio of the first composition to the second composition may be in the range of 3 to 1 to about 40 to 1. Preferably, the ratio of the first composition to the second composition is about 10 to 1.

Also provided is method for anchoring a material in or to concrete or masonry that comprises the steps of delivering the above-described anchor composition to concrete or masonry, the material to be anchored to the concrete or masonry or both; contacting the material to be anchored, the concrete or masonry and the anchor composition; and polymerizing the anchor composition.

The delivery of the anchor composition may be accomplished by any method known to those skilled in the art, including by cartridge in a dispensing gun, by glass capsules or from bulk containers through meter-mix equipment. The composition is applied to either the concrete or masonry, the material to be anchored in or to the concrete or masonry, or both. Then, the concrete or masonry and the material to be anchored to the concrete or masonry are contacted so that both the concrete or masonry and the material to be anchored comes into contact with the anchor composition. The anchoring composition is then polymerized.

The following examples are provided to illustrate particular embodiments of the invention and are not intended to limit the scope of the invention or the claims is any manner.

EXAMPLES Experimental Protocols

Preparation of Anchor Compositions to be Dispensed From a Cartridge using a Dispensing Gun

The appropriate amounts of methacrylate ester polymer and methacrylate ester monomer are weighed. The monomer is added to a container and the polymer is slowly added, with mixing. It is preferred if the monomer and polymer solution are mixed using a disperser, and then further mixed on a jar mill at 3-5 rpm for between 24-48 hours.

To an appropriate amount of the above monomer/polymer solution is added inhibitor, activator, chain transfer agent, fragrance and other ingredients. The composition is mixed, preferably using a disperser. Next, the thixotropic agent is added with shear mixing followed by addition of the filler. If more than one filler is to be included in the anchor composition, it is preferable to add the first filler, then mix, then add the second filler and so on until the desired number of fillers have been added to the composition.

To make a two component composition, each component may be made separately according to the above-described procedure.

Preparation of Anchor Compositions to be Dispensed From a Glass Capsule

The appropriate mounts of methacrylate ester polymer and methacrylate ester monomer are weighted. The monomer is added to a container and the polymer is slowly added, with mixing. It is preferred if the monomer and polymer solution are mixed using a disperser and then further mixed on a jar mill at 3-5 rpm for between 24-48 hours. Inhibitor and activator are added, with mixing, as desired.

The free radical catalyst, typically a peroxide, is introduced into a small glass tube (inner tube), which is then sealed. The sealed small glass tube is placed into a large glass tube (outer tube) that has been sealed at one end. The above-described polymer/monomer solution and any filler is added to the large glass tube and the large glass tube is sealed.

Pull Out Performance

Medium Weight Concrete Block

A medium weight concrete block that was approximately 4"×8"×16", which was free of surface moisture was used. Typically, five replicate pull out tests were run for each adhesive composition tested.

First, three equally spaced 65 mm deep holes were drilled in the 8"×16" side of the concrete block. Then, the holes were cleaned with a brush, with compressed air and a vacuum. An adhesive composition was injected into the drilled holes, and a 1/4"-20×5" stainless steel rod type 304 is inserted into the adhesive-containing hole with a twisting motion. The time before pull out testing (also called cure time) was in the range of about 2 hours to about 72 hours. The stainless steel rod was then connected to an Instron universal tester, Model TTC, Instron Corporation, Canton, Mass, and the rods were pulled at 0.2"/minute until failure. The maximum load and failure type was then recorded. Preferably, in an acceptable anchor composition, the pull out performance is about 2200 (lbs) or greater in concrete block. Most preferably, the material that has been anchored to the concrete or masonry, or the concert or masonry itself fails before the adhesive composition.

Medium Weight Hollow Concrete Block

A 6"×8"×16" (1" wall thickness) medium weight hollow concrete block, free of surface dampness, was drilled with two 16 mm holes on the 8"×16" side of the block (four total). The holes were cleaned of dust, and 16 mm polyethylene screens were installed in the holes. The adhesive composition is injected into the screen to fill the screen, and a 10 mm rod is inserted into the adhesive in the screen with a twisting motion. The adhesive was allowed to cure, typically for 24 hours. The rod was then pulled on a universal tester at 0.2"/min. until failure of the adhesive, rod or concrete. (16 mm polyethylene screens and 10 mm rods may be obtained from SPIT, Valence, France.)

5,000 psi Compressive Strength Concrete

A 3'×6'×12' to 18" deep 4,000-5,000 psi concrete slab, which was cured at least 28 days, and which was free of surface moisture, was drilled with holes. The holes were spaced in the concrete in accordance with ASTM E488-90. The holes were cleaned, and adhesive was injected into the holes followed by the insertion of Grade 5 zinc plated rods with a chrome seal. The adhesive was cured for a period, typically 2 to 24 hours, and the rods were then pulled using a hydraulic jack until failure of the adhesive, rod or concrete.

Torque Performance

A hollow medium weight concrete block having dimensions 6"×8"×16" (1 inch wall thickness), free of surface dampness, was drilled with 2 16 mm holes in each hollow cavity on the 8"×16" side of the block (four total). The holes were cleaned and then a 16 mm polyethylene screen, which are known to those skilled in the art, was inserted into the holes. An adhesive composition was injected to fill the screens, and a 10 mm rod was inserted into the screens containing the adhesive. The adhesive was allowed to cure for a certain time and then a 1/4" thick steel plate with a hole was placed over the rod. A washer was installed and a nut was hand tightened on the rod. The nut was torqued clockwise with a socket wrench and torque transducer until failure of the rod, concrete or adhesive.

It should be noted that three types of concrete blocks that are known to those skilled in the art have been used in the various examples set forth below: medium weight concrete block; 5,000 psi compressive strength concrete; and medium weight hollow concrete block. Unless specified otherwise, "concrete block" or "concrete" shall mean medium weight concrete block.

Materials

The following table shows materials, specific chemical compositions, tradenames, suppliers and locations of the suppliers for the various materials. This list is intended to be illustrative of various materials and should not be construed as limiting the specification or the claims in any manner.

    __________________________________________________________________________                     Trade                                                          Material                                                                               Composition                                                                            Name   Supplier                                                                              Location                                         __________________________________________________________________________     PMMA 2016                                                                              Methyl/ Elvacite ®                                                                        ICI Acrylics                                                                          Wilmington, DE                                           n-butyl 2016                                                                   methacrylate                                                                   Copolymer                                                              PMMA 2008                                                                              Polymethyl                                                                             Elvacite ®                                                                        ICI Acrylics                                                                          Wilmington, DE                                           methacrylate                                                                           2008                                                           PMMA 2010                                                                              Polymethyl                                                                             Elvacite ®                                                                        ICI Acrylics                                                                          Wilmington, DE                                           methacrylate                                                                           2010                                                           PMMA 2021                                                                              Polymethyl                                                                             Elvacite ®                                                                        ICI Acrylics                                                                          Wilmington, DE                                           methacrylate                                                                           2021                                                           MMA     Methyl         ICI Acrylics                                                                          Wilmington, DE                                   Monomer methacrylate                                                           HET     N,N-bis(2-     RSA Corp.                                                                             Danbury, CT                                              hydroxyethyl)-                                                                 p-toluidine                                                            Dodecyl                Aldrich                                                                               Milwaukee, WI                                    Mercaptan              Chemical                                                Tamsil ™ 8                                                                          Silica  Tamsil ™ 8                                                                         Unimin Elco, IL                                                 (2 micron)     Specialty                                                                      Minerals                                                F55 Silica                                                                             Silica Sand (ca.                                                                              U.S. Silica                                                                           Ottawa, IL                                       Sand    200 microns)                                                           ATH 00 20774                                                                           Treated        Nyco   Willsboro, NY                                            alumina        Minerals                                                        Trihydrate     Inc.                                                            (8 micron)                                                             Quartz 1/2                                                                             Quartz 1/2     Agsco Corp.                                                                           Wheeling, IL                                             (ca. 150                                                                       micron)                                                                Huber   Alumina        Huber Solem                                                                           Norcross, GA                                     SB-30-SP                                                                               Trihydrate     Division                                                        (ca. 50                                                                        micron)                                                                ATH 21 20774                                                                           Treated        Nyco   Willsboro, NY                                            Alumina        Minerals                                                        Trihydrate     Inc.                                                            (2 micron)                                                             AFR 400 Di-benzoyl     ATOCHEM                                                                               Buffalo, NY                                              peroxide in    North                                                           Plasticizer    America                                                         (40% BPO)                                                              ANS     Di-benzoyl     ATOCHEM                                                                               Buffalo, NY                                              peroxide in    North                                                           Plasticizer    America                                                         (55% BPO)                                                              CAB-O-SIL ®                                                                        Fumed          Cabot Corp.,                                                                          Tuscola, IL                                      M5      Amorphous      Cab-O-Sil                                                       Silica         Division                                                Aerosil ®                                                                          Treated Fumed                                                                          Aerosil R202                                                                          Degussa                                                                               Ridgefield Park, NJ                              R202    Silica                                                                 Fragrance-             Atlanta                                                                               Kennesaw, GA                                     16322                  Fragrance                                               TMHQ    Trimethyl      Aldrich                                                                               Milwaukee, WI                                            Hydroquinone   Chemical                                                Caddox  Dibenzoyl      Akzo   Dobbs Ferry, NY                                  BFF 50  Peroxide       Chemicals                                                                      Inc.                                                    Quartz #4              Agsco Corp.                                                                           Wheeling, IL                                     __________________________________________________________________________      BPO is dibenzyol peroxide.                                               

Examples of Adhesive Compositions EXAMPLE 1

    ______________________________________                                                             % by Weight of                                             First Composition*  First Composition                                          ______________________________________                                         MMA monomer/MMA polymer                                                                            39.85                                                      solution                                                                       (20% Elvacite ® 2021 in MMA)                                               Quartz 1/2          53.4                                                       Dodecyl mercaptan   0.5                                                        Trimethyl hydroquinone                                                                             0.0161                                                     Silica (Aerosil ® R202)                                                                        5.4                                                        N,N-bis(2-hydroxyethyl)-p-                                                                         0.5                                                        toluidine                                                                      Fragrance-16332     0.35                                                       ______________________________________                                                             % By Weight Of                                             Second Composition* Second Composition                                         ______________________________________                                         Di-benzoyl peroxide 50                                                         (AFR 400-40% di-benzoyl                                                        peroxide)                                                                      Silica (Tamsil ™ 8)                                                                             30                                                         Quartz 1/2          20                                                         ______________________________________                                          *Pigments were added to both the first composition and the second              composition. The first composition contained about 0.02% American Colors       VC10000 white, and the second composition contained about 1% of American       Colors VC50457 rust. The abovedescribed anchor composition is preferably       dispensed by a dispensing gun or by bulk dispensation using metermix           equipment.                                                               

EXAMPLE 2

    ______________________________________                                                             % By Weight                                                Composition         Of Composition                                             ______________________________________                                         Large Glass Tube                                                               MMA monomer/MMA polymer                                                                            22.10                                                      solution                                                                       (20% Elvacite ® 2021 in MMA)                                               N,N-bis(2-hydroxyethyl)-p-                                                                         0.67                                                       toluidine                                                                      Quartz #4           41.78                                                      Small Glass Tube                                                               Di-benzoyl peroxide 1.37                                                       (Cadox BFF50)*                                                                 Glass               34.08                                                      ______________________________________                                    

The above-described anchor composition is preferably dispensed by a glass capsule. The glass is supplied by the small and large glass tubes that hold the composition when the delivery system is crushed.

EXAMPLE 3

    ______________________________________                                                           % by Weight of                                               First Composition First Composition                                            ______________________________________                                         PMMA 2021         9.0                                                          MMA Monomer       20.9                                                         HET               0.3                                                          ATH 21 20774      29.9                                                         Quartz 1/2        39.9                                                         ______________________________________                                                           % by Weight of                                               Second Composition                                                                               Second Composition                                           ______________________________________                                         AFR 400           50                                                           Quartz 1/2        20                                                           ATH 21 20774      30                                                           Pull Out (lbs) - 72 hour cure                                                                    2830                                                         ______________________________________                                    

The first composition and the second composition were combined in a ratio of 10:1 respectively. The pull out performance was measured in medium weight concrete block.

EXAMPLE 4

This example shows various compositions that may be used in practicing the present invention.

    ______________________________________                                                         Composition                                                                   1      2      3        4                                        ______________________________________                                         Type of PMMA     2021     2008   2021   2021                                   % Polymer in Monomer                                                                            10       55     30     20                                     % Polymer Solution                                                                              39.73    88.2   27.2   38.8                                   Filler-Quartz 1/2                                                                               53       10.3   36.3   51.8                                   Filler-Nyco ATH 21               36.3                                          Thixotropic Agent                                                                               5.3      0.5           9.1                                    Pull out in Concrete Block                                                                      2410     2200   2605   2510                                   (lbs)                                                                          ______________________________________                                    

The above compositions were injected into concrete block using a dispensing gun containing a coaxial cartridge. In each composition, HET was used as a catalyst activator (0.5 to 1.3%). Dodecyl mercaptan was used as a chain transfer agent in compositions 1 and 2 (0.5%), and Aerosil® R202 was used as a thixotropic agent, except for composition 4, which used Attagel 50. The compositions were dispensed in a ratio of 10 parts of the above described compositions to 1 part activator. The activator comprised 50% AFR 400, 20 Quartz 1/2 and 30% Tamsil™ 8. The pull out performance was measured in medium weight concrete block after a cure time of between 24-72 hours. In general, a pull out performance of 2200 lbs or greater in medium weight concrete block is required.

Comparative Examples EXAMPLE 5

Table 1 below compares a commercially available anchor adhesive product, Ready Fix, which is based on aromatic polyesters, with commercially available structural adhesives based on acrylates having no inorganic particulate filler.

                  TABLE 1                                                          ______________________________________                                         Composition    Pull Out (lbs)                                                  ______________________________________                                         Ready Fix      2160                                                            Plexus MA 300  400                                                             Plexus MA 310  850                                                             Plexus MA 320  260                                                             ______________________________________                                          Ready Fix may be obtained from Red Head, Scotland.                             Plexus MA 300, Plexus MA 310, and Plexus MA 320 may be obtained from ITW       Adhesive Systems, Danvers, MA.                                           

Table 1 shows that the pull out performance of the commercially available acrylate structural adhesives are below the pull out performance acceptable for an anchor adhesive.

EXAMPLE 6

Table 2 below shows the pull out performance of anchor compositions containing methyl methacrylate polymers of various weight average molecular weights. Each composition contained about 99.75% of a PMMA/JMMA solution. The compositions were mixed to a viscosity of approximately 4000 to 10,000 centipoise. (Viscosities were measured on a Brookfield viscometer using an HA6 spindle at 10 rpm at 23° C.) Each solution also contained 0.25% HET and 5% ANS (40% BPO). No fillers were used. Each of the compositions were mixed by hand and injected into concrete block using a dispensing gun containing a one component cartridge.

                  TABLE 2                                                          ______________________________________                                                    PMMA       PMMA     PMMA   PMMA                                     Polymer    2016       2008     2010   2021                                     ______________________________________                                         Polymer Type                                                                              Methyl/n-  Homo-    Homo-  Homo-                                               butyl      polymer  polymer                                                                               polymer                                             methacrylate                                                                   copolymer                                                           Polymer Weight                                                                            60,000     36,000   84,000 118,000                                  Average                                                                        Molecular Weight                                                               Pull Out   1120       1250     1380   1700                                     (lbs) - 72 hr cure                                                             ______________________________________                                    

The data show that as the molecular weight of the polymer increases, the pull out strength also increases. The data also show that the pull out strength of the homopolyers (PMMA 2008, 2010 and 2021) was larger than the copolymer (PMMA 2016).

EXAMPLE 7

Table 3 below shows the pull-out performance of anchor compositions containing various types and sizes of fillers. Each anchor composition contains a solution of PMMA/MMA mixed to have a viscosity of about 4000 centipoise (Viscosities were measured on a Brookfield viscometer using an HA6 spindle at 10 rpm at 23° C.), 0.17-25% HET and 3-6% ANS (40% BPO). In addition, compositions 3 and 4 contain 0.6 to 1.0% CAB-O-SIL® M5.

                                      TABLE 3                                      __________________________________________________________________________                  PMMA PMMA PMMA PMMA PMMA PMMA                                     Polymer      2016 2016 2016 2021 2021 2021                                     __________________________________________________________________________     % PMMA/MMA Solution                                                                         67.0 49.9 59.3 39.6 33.1 29.9                                     Filler 1     2    8    200  200  50   150                                      Size (microns)                                                                 Filler 1     32.8 49.9 39.5 59.6 66.6 39.9                                     wt %                                                                           Filler 2:                             8                                        Size (microns)                                                                 Filler                                29.9                                     wt %                                                                           Pull Out (lbs) -                                                                            1530 1620 2210 2580 2540 2600                                     72 hr. cure                                                                    __________________________________________________________________________

Pull out was conducted using medium weight concrete blocks.

    ______________________________________                                         Size (microns)      Filler                                                     ______________________________________                                         2                   Tamsil ™ 8                                              8                   ATH 00 20774                                               200                 F55 Silica Sand                                            50                  Huber SB-30-SP                                             150                 Quartz 1/2                                                 ______________________________________                                    

Each of the compositions were mixed by hand and injected using a dispensing gun containing a one component cartridge.

To get the desired pull out performance, the anchor composition of the present invention includes an inorganic, insoluble, inert filler. Table 3 shows that the pull out strength of an anchoring composition increases with increased particles size of the filler.

EXAMPLE 8

    ______________________________________                                         Pull Out Performance in 5,000 psi Compressive Strength Concrete                                        Composition of                                                       Ready Fix Example 1*                                             ______________________________________                                         Pull Out (lbs)                                                                               5800      6000                                                   2 hr cure                                                                      Pull Out (lbs)                                                                               7100      7200                                                   24 hr cure                                                                     ______________________________________                                         Pull Out and Torque Performance in Hollow Concrete Blocks                                              Composition of                                                       C-Mix 3000                                                                               Example 1*                                             ______________________________________                                         Pull Out (lbs)                                                                               1080      1310                                                   24 hr cure                                                                     Torque (ft-lbs)                                                                              18.1      20.3                                                   24 hr cure                                                                     ______________________________________                                          C-Mix 3000 is a commercially available aromatic polyester anchor adhesive      which can be obtained from SPIT, France.                                       *Compositions were the same as those of Example 1, except that no              fragrance was added.                                                     

The composition of Example 1 above was compared to commercial products in 5,000 psi compressive strength concrete and in 55/8×75/8×155/8 inch hollow concrete block. The performance of the composition of Example 1 is equivalent or superior to commercial adhesives based on aromatic polyesters and aromatic vinyl esters.

EXAMPLE 9

The following example compares a commercially available anchor adhesive that is delivered using a glass capsule with compositions of the present invention, which are delivered using a glass capsule. Each of anchor composition A and B comprised 21.9% PMMA/MMA solution, 41.3% quartz 4, 0.88% HET, 1.8% Lucidol CH50 BPO and 33.7% glass (from the glass capsule, which acts as a filler when crushed). Table 4 below shows the pull out strengths of the various compositions in 5,000 psi compressive strength concrete.

                  TABLE 4                                                          ______________________________________                                                                   A       B                                            Polymer       Hilti HEA   2021    2008                                         ______________________________________                                         % polymer in solution       20    30                                           Dodecyl mercaptan (%)             0.43                                         Pull Out (lbs) -                                                                             16600       13130   16600                                        1 hour                                                                         Pull Out (lbs) -                                                                             16800       14530   16700                                        24 hour                                                                        ______________________________________                                          Hilti HEA can be obtained from the Hilti Corporation, Tulsa, OK.               Lucidol CH50 can be obtained from ATOCHEM, Buffalo, NY.                   

What is claimed is:
 1. A system for anchoring bolts in structural bodies comprising:(a) a structural body selected from the group consisting of concrete bodies, masonry bodies and rock; (b) an anchor bolt; and (c) a cured polymer composition adhesively contacting said structural body and said bolt, said cured polymer composition providing a pull-out force of at least about 2200 lbs. in medium weight concrete block and having been cured from a curable composition comprising:i. from about 20% to about 90% by weight of a solution of methacrylate ester polymer in methacrylate ester monomer; ii. inorganic filler; iii. free-radical catalyst; and iv. trimethyl hydroquinone as a free-radical inhibitor.
 2. The system of claim 1 wherein said structural body is a concrete block and said anchoring bolt is a steel rod.
 3. The system of claim 1 wherein said curable composition further comprises a free radical accelerator.
 4. The system of claim 1 wherein the polymer comprises about 10% to about 60% of the solution.
 5. The system of claim 1 wherein the filler comprises from about 10% to about 75% by weight of the entire composition.
 6. The system of claim 1 wherein the curable composition further comprises from about 0.5% to about 10% by weight of the entire composition of a thixotropic agent.
 7. The system of claim 1 wherein the curable composition further comprises a chain transfer agent.
 8. The system of claim 3 wherein the free radical accelerator is N,N-bis(2-hydroxyethyl)-p-toluidine.
 9. The system of claim 1 wherein the filler is quartz, sand, glass or alumina trihydrate.
 10. The system of claim 1 wherein said anchor bolt is a reinforcing member.
 11. The system of claim 1 wherein said anchor bolt is metallic.
 12. The system of claim 1 wherein said anchor bolt comprises means for attaching objects to said structural body.
 13. A method for anchoring bolts in structural bodies comprising:(a) providing a structural body selected from the group consisting of concrete bodies, masonry bodies and rock; (b) delivering to said structural body a curable adhesive composition comprising:i. from about 20% to about 90% by weight of a solution of methacrylate ester polymer in methacrylate ester monomer; ii. inorganic filler; iii. free-radical catalyst; and iv. trimethyl hydroquinone as a free-radical inhibitor; (c) contacting said curable composition with an anchor bolt; and (d) curing said adhesive composition to produce a cured composition which provides a pull-out force of at least about 2200 lbs. in medium weight concrete block.
 14. The method of claim 13 wherein said structural body is a concrete block and said anchor bolt is a steel rod.
 15. The system of claim 1 wherein said structural body is a concrete block and said anchor bolt is a steel rod.
 16. The method of claim 13 wherein said curable composition further comprises a free-radical accelerator.
 17. The method of claim 13 wherein the monomer/polymer solution comprises from about 3% to about 6% by weight of the entire composition.
 18. The method of claim 13 wherein the polymer comprises about 10% to about 60% of the solution.
 19. The method of claim 13 wherein the filler comprises from about 10% to about 75% by weight of the entire composition.
 20. The method of claim 13 wherein the curable composition further comprises from about 0.5% to about 10% by weight of the entire composition of a thixotropic agent.
 21. The method of claim 13 wherein the curable composition further comprises a chain transfer agent.
 22. The method of claim 13 wherein the free-radical catalyst is a peroxide.
 23. The method of claim 22 wherein the peroxide is benzoyl peroxide.
 24. The method of claim 13 wherein the filler is quartz, sand, glass or alumina trihydrate.
 25. The method of claim 13 wherein said anchor bolt is a reinforcing member.
 26. The method of claim 13 wherein said anchor bolt is metallic.
 27. The method of claim 13 wherein said anchor bolt comprises means for attaching objects to said structural body.
 28. The method of claim 16 wherein said free-radical accelerator is N,N-bis(2-hydroxyethyl)-p-toluidine. 